EP0096122A1 - Plaque renforcée en sulfure de polyphénylène, plaque de circuit imprimé ainsi fabriquée et procédé de leur fabrication - Google Patents

Plaque renforcée en sulfure de polyphénylène, plaque de circuit imprimé ainsi fabriquée et procédé de leur fabrication Download PDF

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Publication number
EP0096122A1
EP0096122A1 EP82302887A EP82302887A EP0096122A1 EP 0096122 A1 EP0096122 A1 EP 0096122A1 EP 82302887 A EP82302887 A EP 82302887A EP 82302887 A EP82302887 A EP 82302887A EP 0096122 A1 EP0096122 A1 EP 0096122A1
Authority
EP
European Patent Office
Prior art keywords
printed circuit
polyphenylene sulfide
glass fibers
molded board
preparation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP82302887A
Other languages
German (de)
English (en)
Other versions
EP0096122B1 (fr
Inventor
Minoru Kitanaka
Yukichi Deguchi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toray Industries Inc
Original Assignee
Toray Industries Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toray Industries Inc filed Critical Toray Industries Inc
Priority to DE8282302887T priority Critical patent/DE3273422D1/de
Priority to EP82302887A priority patent/EP0096122B1/fr
Publication of EP0096122A1 publication Critical patent/EP0096122A1/fr
Application granted granted Critical
Publication of EP0096122B1 publication Critical patent/EP0096122B1/fr
Expired legal-status Critical Current

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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/003Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts characterised by the matrix material, e.g. material composition or physical properties
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00Layered products comprising a layer of metal
    • B32B15/04Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/28Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00Ancillary operations in connection with laminating processes
    • B32B38/0036Heat treatment
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00Use of ingredients characterised by shape
    • C08K7/02Fibres or whiskers
    • C08K7/04Fibres or whiskers inorganic
    • C08K7/14Glass
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00Printed circuits
    • H05K1/02Details
    • H05K1/03Use of materials for the substrate
    • H05K1/0313Organic insulating material
    • H05K1/032Organic insulating material consisting of one material
    • H05K1/0333Organic insulating material consisting of one material containing S
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2309/00Use of inorganic materials not provided for in groups B29K2303/00 - B29K2307/00, as reinforcement
    • B29K2309/08Glass
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10Inorganic fibres
    • B32B2262/101Glass fibres
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00Electrical equipment
    • B32B2457/08PCBs, i.e. printed circuit boards
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00Printed circuits
    • H05K1/02Details
    • H05K1/03Use of materials for the substrate
    • H05K1/0313Organic insulating material
    • H05K1/0353Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0366Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/02Fillers; Particles; Fibers; Reinforcement materials
    • H05K2201/0203Fillers and particles
    • H05K2201/0242Shape of an individual particle
    • H05K2201/0251Non-conductive microfibers

Definitions

  • This invention relates to a reinforced polyphenylene sulfide (hereinafter referred to as "PPS" for brevity) molded board which is excellent in the mechanical I properties such as the impact resistance and the thermal properties such as the heat distortion temperature and solder resistance, and which provides a very strong adhesion to a metallic foil even without using an adhesive.
  • PPS polyphenylene sulfide
  • This invention also relates to a printed circuit board comprising such a reinforced PPS molded board as an insulating substrate, and a process for preparing this printed circuit board with ease and at low costs.
  • So-called printed circuit boards comprising an insulating substrate and a conductor composed of a metallic foil such as a copper foil, which is flatly bonded onto the substrate, are used in large quantities for electric circuits in various household electric appliances, electronic computers, communication facilities and various meters and instruments.
  • thermosetting resin such as an epoxy resin, a phenol resin or an unsaturated polyester resin
  • base sheet composed of paper, glass fibers or synthetic fibers.
  • These composite sheets are prepared by a process wherein a base sheet composed of paper, glass fibers or synthetic fibers is coated or impregnated with a resin solution so-called "varnish", which is formed by dissolving a thermosetting resin in a solvent; the coated or impregnated base sheet is heated in a drier, thereby to vaporize the solvent in the varnish and remove the solvent and to effect polymerization of the resin to form a prepreg of the so-called B-stage; a predetermined number of the so-formed prepregs are superposed upon another and compressed under heating to cure the resin.
  • a resin solution so-called "varnish" which is formed by dissolving a thermosetting resin in a solvent
  • the coated or impregnated base sheet is heated in a drier, thereby to vaporize the solvent in the varnish and remove the solvent and to effect polymerization of the resin to form a prepreg of the so-called B-stage; a predetermined number of the so-formed prepregs are
  • thermoplastic resin such as polyethylene, polytetrafluoroethylene or polyphenylene oxide may also be used as the insulating substrate for a printed circuit board.
  • thermoplastic resins can provide printed circuit boards which are satisfactorily balanced among the thermal properties, the mechanical properties, the chemical resistance and the manufacturing costs.
  • JP-A Japanese Patent Laid-open Application
  • JP-A Japanese Patent Laid-open Application
  • JP-A Japanese Patent Laid-open Application
  • No. 85,380/79 proposes a printed circuit board comprising as an insulating substrate a molded board comprising PPS, which is excellent by itself in the heat resistance, the chemical resistance, the electric properties and the flame retardancy, and glass fibers (hereinafter referred to as "GF" for brevity) having a length smaller than 3 mm, and a metallic foil bonded to said substrate through an epoxy type adhesive.
  • this printed circuit board is poor in the mechanical properties and is especially poor in the resistance to the soldering operation indispensable for processing and attachment of the printed circuit board, that is, the solder resistance.
  • the process for preparing this printed circuit board involves various complicated steps such as the steps of mixing PPS with GS , the melt-kneading step, the injection molding step, the adhesive-coating step and the metal foil-bonding step, and the obtained printed circuit board is very expensive.
  • Another object of the present invention is to provide a process for preparing the above-mentioned excellent printed circuit board at low costs by simplified process steps.
  • a reinforced polyphenylene sulfide molded board comprising, based on the weight of the molded board, 20 to 85% by weight of polyphenylene sulfide and 15 to 80% by weight of glass fibers having a length of at least 5 mm.
  • a printed circuit board comprising as an insulating substrate a glass fiber--reinforced polyphenylene sulfide molded board comprising, based on the weight of the molded board, 20 to 85% by weight of polyphenylene sulfide having a degree of crystallinity of at least 40% and 15 to 80% by weight of glass fibers having a length of at least 5 mm, and a metallic foil bonded to the surface of said insulating substrate.
  • a process for the preparation of printed circuit boards which comprises compressing under heating a mixture or laminate comprising 20 to 85% by weight of polyphenylene sulfide and 15 to 80% by weight of glass fibers having a length of at least 5 mm to form a composite molded board, and, at or after the compression step, bonding a metallic foil to the surface of the molded board.
  • the printed circuit board of the present invention is prepared from PPS and GF without subjecting the mixture of PPS and GF to the melt-kneading step, the process steps can be simplified, and since GF contained in the obtained printed circuit board retains a length of at least 5 mm, the reinforcing efficiency is high and the mechanical properties such as the impact resistance are very high. Furthermore, the printed circuit board of the present invention is excellent in the solder resistance over the conventional printed circuit board comprising as an insulating substrate a PPS molded board comprising GF having a length smaller than 3 mm, and therefore, an effect of providing a high adhesion between the substrate and metallic foil without using an adhesive can be attained according to the present invention.
  • PPS that is used in the present invention is a polymer comprising at least 90 mol %, preferably at least 95 mol %, of repeating units represented by the structural formula
  • PPS that is used in the present invention may comprise up to.10 mol % of repeating units represented by the structural formula:
  • PPS used in the present invention should have a melt viscosity of 50 to 50,000 poises, especially 100 to 5,000 poises, as determined at a temperature of 300°C and an apparent shear rate of 200 sec -1 . If the melt viscosity is lower than 50 poises, satisfactory mechanical strength and impact resistance cannot be obtained. If the melt viscosity is higher than 50,000 poises, when GF is combined with PPS, voids among GF are not sufficiently filled with PPS and attainment of the desired mechanical strength cannot be expected.
  • ordinary additives such as an antioxidant, a heat stabilizer, a lubricant, a crystal nucleating agent, an ultraviolet absorber, a coloring agent, a filler and a parting agent may be incorporated into PPS used in the present invention. Furthermore, a small amount of other polymer may be blended in PPS used in the present invention, so far as attainment of the objects of the present invention is not inhibited.
  • GF used in the present invention is not particularly limited, so far as the length of GF is at least 5 mm.
  • GF may be used in the form of a chopped fiber, a chopped fiber mat, a continuous filament mat, a woven fabric, a knitted fabric or a combination of two or more of them.
  • the degree of crystallinity of the PPS matrix in the insulating substrate be at least 40%, especially at least 50%. This degree of crystallinity is important in the case where the glass fiber-reinforced PPS molded board is used as an insulating substrate of a printed circuit board. This is because, if the degree of crystallinity is lower than 40%, deformation is large under heating and the heat resistance is insufficient. It is preferred that the degree of crystallinity be not i pore than about 75%. If the degree of crystallinity exceeds about 75 % , a substantially long period of time is necessary for crystallization.
  • the length of GF is shortened to less than 3 mm, particularly less than 0.5 mm, by a shearing force imposed at the melt-kneading or injection molding step, and therefore, the resulting molded board becomes poor in impact strength, and comes to have anisotropic characteristics and readily warp.
  • the printed circuit board prepared according to the simplified process of the present invention has excellent thermal and mechanical properties and a good solder resistance, and therefore, application of this printed circuit board to electric and electronic industries is very promising.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Mathematical Physics (AREA)
  • Composite Materials (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Thermal Sciences (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Reinforced Plastic Materials (AREA)
EP82302887A 1982-06-04 1982-06-04 Plaque renforcée en sulfure de polyphénylène, plaque de circuit imprimé ainsi fabriquée et procédé de leur fabrication Expired EP0096122B1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
DE8282302887T DE3273422D1 (en) 1982-06-04 1982-06-04 Reinforced polyphenylene sulphide board, printed circuit board made therefrom and process for making them
EP82302887A EP0096122B1 (fr) 1982-06-04 1982-06-04 Plaque renforcée en sulfure de polyphénylène, plaque de circuit imprimé ainsi fabriquée et procédé de leur fabrication

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP82302887A EP0096122B1 (fr) 1982-06-04 1982-06-04 Plaque renforcée en sulfure de polyphénylène, plaque de circuit imprimé ainsi fabriquée et procédé de leur fabrication

Publications (2)

Publication Number Publication Date
EP0096122A1 true EP0096122A1 (fr) 1983-12-21
EP0096122B1 EP0096122B1 (fr) 1986-09-24

Family

ID=8189692

Family Applications (1)

Application Number Title Priority Date Filing Date
EP82302887A Expired EP0096122B1 (fr) 1982-06-04 1982-06-04 Plaque renforcée en sulfure de polyphénylène, plaque de circuit imprimé ainsi fabriquée et procédé de leur fabrication

Country Status (2)

Country Link
EP (1) EP0096122B1 (fr)
DE (1) DE3273422D1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0229495A1 (fr) * 1985-12-12 1987-07-22 Tosoh Corporation Composition de résine de poly(sulfure de phénylène) utilisable comme revêtement
EP0491535A2 (fr) * 1990-12-17 1992-06-24 Polyplastics Co. Ltd. Compositions de résine de polysulfure d'arylène ayant une excellente adhésion et procédé pour leur préparation
US5227427A (en) * 1990-12-17 1993-07-13 Polyplastics Co., Ltd. Polyarylene sulfide resin composition and process for the preparation of the same
EP0697280A1 (fr) * 1994-06-24 1996-02-21 General Electric Company Structures stratifiées thermoformables et méthodes de fabrication

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3953653A (en) * 1975-04-30 1976-04-27 Phillips Petroleum Company Method to treat a poly(arylene sulfide) surface
US4017450A (en) * 1976-03-29 1977-04-12 Phillips Petroleum Company Inhibition of poly(arylene sulfide) resin induced metal corrosion
US4115344A (en) * 1977-07-05 1978-09-19 Phillips Petroleum Company Mold corrosion inhibition in poly(arylene) sulfide processing

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3953653A (en) * 1975-04-30 1976-04-27 Phillips Petroleum Company Method to treat a poly(arylene sulfide) surface
US4017450A (en) * 1976-03-29 1977-04-12 Phillips Petroleum Company Inhibition of poly(arylene sulfide) resin induced metal corrosion
US4115344A (en) * 1977-07-05 1978-09-19 Phillips Petroleum Company Mold corrosion inhibition in poly(arylene) sulfide processing

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 97, no. 76, 1982, page 735, no. 173581w, Columbus Ohio (USA); & JP - A - 82 96 588 (TORAY INDUSTRIES INC.) (15-06-1982) *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0229495A1 (fr) * 1985-12-12 1987-07-22 Tosoh Corporation Composition de résine de poly(sulfure de phénylène) utilisable comme revêtement
EP0491535A2 (fr) * 1990-12-17 1992-06-24 Polyplastics Co. Ltd. Compositions de résine de polysulfure d'arylène ayant une excellente adhésion et procédé pour leur préparation
EP0491535A3 (en) * 1990-12-17 1992-11-04 Polyplastics Co. Ltd. Polyarylene sulfide resin composition excellent in adhesion and process for the preparation of the same
US5227427A (en) * 1990-12-17 1993-07-13 Polyplastics Co., Ltd. Polyarylene sulfide resin composition and process for the preparation of the same
EP0697280A1 (fr) * 1994-06-24 1996-02-21 General Electric Company Structures stratifiées thermoformables et méthodes de fabrication
US5895709A (en) * 1994-06-24 1999-04-20 General Electric Company Multi-layer thermoformable laminates and methods of their manufacture

Also Published As

Publication number Publication date
DE3273422D1 (en) 1986-10-30
EP0096122B1 (fr) 1986-09-24

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